TWI495689B

TWI495689B - Elastomeric films and gloves

Info

Publication number: TWI495689B
Application number: TW102109757A
Authority: TW
Inventors: Khon Pu Foo
Original assignee: Diptech Pte Ltd
Priority date: 2005-07-20
Filing date: 2006-07-10
Publication date: 2015-08-11
Also published as: JP5478879B2; US20080139723A1; JP6239555B2; US8680191B2; US20100175164A1; HK1112633A1; MY147739A; EP1904569B1; RU2008106479A; US20130232663A1; CA2616921A1; EP1904569A1; RU2545541C2; PL1904569T3; TWI434892B; ES2417059T3; RU2394853C2; AU2005334524A2; DK1904569T3; JP2014088563A

Description

彈性膜及手套Elastic film and gloves

本發明係關於用於製造合成手套之彈性膜之組合物，及形成彈性膜及手套之方法。The present invention relates to a composition for producing an elastic film of a synthetic glove, and a method of forming an elastic film and a glove.

通常已知諸如手套之彈性物品係由天然橡膠製造。普通製造方法涉及將一成形模浸漬於一含有天然橡膠乳膠之貯槽中。然而，由於少量蛋白質會自手套瀝濾至皮膚中，因而橡膠乳膠會引起皮膚過敏反應，所以橡膠乳膠並非用於形成手套之理想材料。It is generally known that elastic articles such as gloves are made of natural rubber. A common manufacturing method involves immersing a forming die in a storage tank containing a natural rubber latex. However, rubber latex is not an ideal material for forming gloves because a small amount of protein is leached from the glove into the skin, and the rubber latex causes an allergic reaction to the skin.

已開發利用合成聚合材料之天然橡膠之替代物。由合成聚合材料製造彈性物品通常涉及一類似方法，即將一鑄模浸漬於一含有合成聚合物之浴槽中，以在該鑄模上沈積一對應於手套所需厚度之層。Alternatives to natural rubber utilizing synthetic polymeric materials have been developed. The manufacture of elastic articles from synthetic polymeric materials typically involves a similar process of immersing a mold in a bath containing a synthetic polymer to deposit a layer on the mold that corresponds to the desired thickness of the glove.

此單一浸漬方法可製造極可能存在或產生諸如脆弱點或針孔之缺陷之彈性膜。視應用而定，當其使穿用者曝露於感染或化學滲透時，此可能造成問題。多次浸漬方法製造多層膜，且可避免或限制諸如此等缺陷之風險，但其通常較厚，且因此敏感性低。若穿用者使用小器具工作，諸如在外科應用中，則此低敏感性會造成問題。This single impregnation method makes it possible to produce an elastic film that is highly likely to present or produce defects such as fragile spots or pinholes. Depending on the application, this can cause problems when it exposes the wearer to infection or chemical penetration. Multiple impregnation methods are used to make multilayer films, and the risk of defects such as these can be avoided or limited, but they are generally thicker and therefore less sensitive. This low sensitivity can cause problems if the wearer is working with a gadget, such as in a surgical application.

需要開發一適用於製造合成手套之彈性膜，其中穿用者具有良好之敏感性，以使穿用者能夠使用小器具舒適地工作，但亦足夠堅固，而不存在或產生缺陷。There is a need to develop an elastic film suitable for use in the manufacture of synthetic gloves wherein the wearer has good sensitivity to enable the wearer to work comfortably with the gadget, but is also sufficiently strong to be free of defects or defects.

由合成聚合材料製造彈性物品亦通常涉及促進劑之使用，此可能引起化學過敏。商業上使用之促進劑係衍生自胺基甲酸酯、雙甲硫羰醯胺或噻唑，且被歸類於IV型過敏原。該等物質會引起過敏接觸性皮炎，其症狀包含紅斑、小泡、丘疹、搔癢、水泡及/或結殼。在彈性物品之製造中，需要處理由該等過敏原之使用而引起之化學過敏問題。The manufacture of elastic articles from synthetic polymeric materials also generally involves the use of accelerators, which can Can cause chemical allergy. Commercially used accelerators are derived from urethane, bis-methylthioketamine or thiazole and are classified as type IV allergens. These substances can cause allergic contact dermatitis, and the symptoms include erythema, vesicles, papules, itching, blisters and/or crusts. In the manufacture of elastic articles, it is necessary to deal with chemical allergy problems caused by the use of such allergens.

本發明提供用於製造彈性膜之組合物、由該等彈性膜製造之合成手套及製造該等手套之方法。The present invention provides compositions for making elastic films, synthetic gloves made from such elastic films, and methods of making such gloves.

在第一態樣中，本發明提供一種用於製造彈性膜之組合物，其包括：合成聚合物，硫，及金屬氧化物交聯劑，其中，該組合物中之總固體濃度(TSC%)係介於組合物之5-20重量%之間，且該組合物不含促進劑。In a first aspect, the present invention provides a composition for making an elastic film comprising: a synthetic polymer, sulfur, and a metal oxide crosslinking agent, wherein the total solids concentration (TSC%) in the composition ) between 5 and 20% by weight of the composition, and the composition contains no promoter.

該組合物宜為該合成聚合物(通常為線性聚合物)於液體(通常為水)中之分散液。該金屬交聯劑藉由離子型交聯合成聚合物中之基團而起作用。舉例而言，當合成聚合物係羧酸化聚丙烯腈丁二烯時，諸如氧化鋅之該金屬氧化物交聯劑藉由離子型交聯羧酸基團而起作用。該硫用於共價型交聯不飽和丁二烯。The composition is preferably a dispersion of the synthetic polymer (usually a linear polymer) in a liquid, usually water. The metal crosslinker acts by ionic bonding to form a group in the polymer. For example, when the synthetic polymer is a carboxylated polyacrylonitrile butadiene, the metal oxide crosslinker such as zinc oxide acts by ionic crosslinking of the carboxylic acid group. This sulfur is used for covalent crosslinking of unsaturated butadiene.

通常，交聯之量決定彈性膜中彈性體之彈性。因此，金屬氧化物交聯劑及硫之量將有助於交聯之程度及最終彈性膜之彈性。因為合成手套通常需要良好之伸長特性以有助於手套之拉伸以適應穿用者之手，所以此係重要的。Generally, the amount of crosslinking determines the elasticity of the elastomer in the elastic film. Therefore, the amount of metal oxide crosslinker and sulfur will contribute to the degree of crosslinking and the elasticity of the final elastic film. This is important because synthetic gloves typically require good elongation characteristics to aid in the stretching of the glove to accommodate the wearer's hand.

彈性膜適用於製造合成手套。因此，在另一態樣中，本發明提供由多層彈性膜製造之合成手套，該彈性膜包括：固化組合物，其包括合成聚合物，硫，及金屬氧化物交聯劑，其中該組合物不含促進劑，及其中，該多層彈性膜之平均厚度係介於約0.01至約0.3 mm之間。Elastomeric membranes are suitable for the manufacture of synthetic gloves. Accordingly, in another aspect, the present invention provides a synthetic glove made from a multilayer elastic film, the elastic film comprising: a cured composition comprising a synthetic polymer, sulfur, and a metal oxide crosslinking agent, wherein the composition contains no promoter, and wherein the multilayer elastic film has an average thickness of between about 0.01 and about 0.3 mm .

在本發明之一實施例中，彈性膜之平均厚度係介於約0.03至約0.08 mm之間。In one embodiment of the invention, the elastic film has an average thickness of between about 0.03 and about 0.08 mm.

在另一態樣中，本發明提供一種製造層狀彈性膜之多次塗覆方法，其包括以下步驟：(i)將一鑄模浸漬於一含有鈣離子之凝結劑中，其中鈣離子之濃度介於1.0至10.0重量%之間；接著(ii)將該經凝結劑浸漬之鑄模乾燥或部分乾燥；(iii)將該經凝結劑塗覆之鑄模浸漬於一用於製造彈性膜之組合物中且停留介於1.0至10.0秒之間之時間以於該鑄模上製造一層彈性膜組合物，其中該組合物包括介於5至20%之間之總固體含量及介於25℃至45℃之間之溫度；(iv)將該彈性膜組合物乾燥；(v)將該鑄模浸漬於一用於製造彈性膜之組合物中且停留介於1.0至10.0秒之間之時間以於該鑄模上製造另一層彈性膜組合物，其中該組合物包括介於5至20%之間之總固體含量及介於25℃至45℃之間之溫度；(vi)視需要重複該乾燥步驟(iv)及該額外之浸漬步驟(v)；及(vii)乾燥並固化該層狀彈性膜，其中每一層之平均厚度係介於6%與90%之間且整體層狀彈性膜之平均厚度係介於約0.01 mm至約0.3 mm之間。In another aspect, the present invention provides a multiple coating method for producing a layered elastic film, comprising the steps of: (i) immersing a mold in a coagulant containing calcium ions, wherein the concentration of calcium ions Between 1.0 and 10.0% by weight; then (ii) drying or partially drying the coagulant-impregnated mold; (iii) immersing the coagulant-coated mold in a composition for producing an elastic film And staying between 1.0 and 10.0 seconds to produce an elastic film composition on the mold, wherein the composition comprises a total solids content between 5 and 20% and between 25 ° C and 45 ° C (iv) drying the elastic film composition; (v) immersing the mold in a composition for producing an elastic film and staying between 1.0 and 10.0 seconds for the mold Making another layer of an elastic film composition, wherein the composition comprises a total solids content of between 5 and 20% and a temperature between 25 ° C and 45 ° C; (vi) repeating the drying step as needed (iv And the additional impregnation step (v); and (vii) drying and curing the layered elastic film, each of which The average thickness of the layers is between 6% and 90% and the average thickness of the overall layered elastic film is between about 0.01 mm and about 0.3 mm.

以上所定義之該多次塗覆方法可利用具有硫之組合物。亦可使用金屬氧化物交聯劑或非金屬氧化物交聯劑，例如亞磺醯胺類化合物、噻唑類化合物、胍類化合物、秋蘭姆類(thiurams)化合物、二硫代胺基甲酸鹽類化合物、二硫代磷酸鹽類化合物、醛類-礦(aldehyde-mine)化合物、亞磺醯亞胺類化合物、硫/硫供體、酚醛硬化劑、苯醌衍生物、雙馬來醯亞胺、三加速劑、胺基甲酸酯交聯劑及過氧化物衍生物。The multiple coating method defined above can utilize a composition having sulfur. Metal oxide crosslinking agents or non-metal oxide crosslinking agents such as sulfinamides, thiazoles, terpenoids, thiurams, dithiocarbamates may also be used. Compounds, dithiophosphates, aldehyde-mine compounds, sulfoximine compounds, sulfur/sulfur donors, phenolic hardeners, benzoquinone derivatives, double malayan Amine, three Accelerator, urethane crosslinker and peroxide derivative.

可向該第一層添加一層以上，意即，步驟(iv)及(v)可重複若干次。最終彈性膜可包括2至15層，較佳2至10層，更佳2至6層之組合物。每一層可為大約相等之厚度，或為不同之厚度。舉例而言，第一層可為50%，第二層為30%，第三層為15%等。藉由改變每一層之組合物之總固體含量及該層沈積之溫度可達成大約相等之厚度。即使% TSC保持在相同水平，每一層亦可發生不同之沈積機制，且可沈積不同之厚度。因此，有時需要改變% TSC以保持相同水平之厚度。亦可根據凝結劑溶液中鈣離子之濃度，改變沈積層之厚度。More than one layer may be added to the first layer, meaning that steps (iv) and (v) may be repeated several times. The final elastic film may comprise a composition of 2 to 15 layers, preferably 2 to 10 layers, more preferably 2 to 6 layers. Each layer can be about equal thickness or a different thickness. For example, the first layer may be 50%, the second layer is 30%, the third layer is 15%, and the like. An approximately equal thickness can be achieved by varying the total solids content of the composition of each layer and the temperature at which the layer is deposited. Even if the % TSC is kept at the same level, different deposition mechanisms can occur for each layer, and different thicknesses can be deposited. Therefore, it is sometimes necessary to change the % TSC to maintain the same level of thickness. The thickness of the deposited layer may also be varied depending on the concentration of calcium ions in the coagulant solution.

如上所述之多次塗覆方法形成一較堅固之膜，其輔助降低諸如針孔及/或脆弱點之缺陷之可能。在製造彈性膜之組合物中所利用之固體的顯著低濃度輔助保持每一塗層為薄的。因此，將總厚度保持在最小值，且就用於製造每一手套之調配物之量而言，此亦輔助保持低成本。The multiple coating process described above forms a relatively strong film that assists in reducing the potential for defects such as pinholes and/or fragile spots. The significantly low concentration of solids utilized in the composition of the elastomeric film assists in keeping each coating thin. Therefore, the total thickness is kept to a minimum, and this also helps to maintain low cost in terms of the amount of formulation used to make each glove.

本發明之彈性膜係適於製造諸如合成拋棄式手套之合成手套。按照慣例，合成拋棄式手套係用於避免污染之場所，意即，在與感染場所接觸時有感染轉移之風險之食物處理中或醫院中。當進行身體檢查時，合成拋棄式手套亦用於避免經由患者與檢查者之間之皮膚接觸的疾病轉移。The elastic film of the present invention is suitable for the manufacture of synthetic gloves such as synthetic disposable gloves. Conventionally, synthetic disposable gloves are used to avoid contamination, i.e., in food processing or in hospitals where there is a risk of infection transfer when in contact with an infected site. Synthetic disposable gloves are also used to avoid disease transfer through skin contact between the patient and the examiner when performing a physical examination.

拋棄式手套通常比非拋棄式手套更薄，其中一更薄之手套之低製造成本乃意謂在一次或若干次使用後丟棄手套係具有成本效益的。Disposable gloves are usually thinner than non-disposable gloves, where a thinner glove is lower Manufacturing costs mean that it is cost effective to discard the gloves after one or several uses.

手套(包含合成拋棄式手套)之物理性質，通常包含一薄彈性膜之適當貼緊配合，以促進穿用者之接觸敏感性。同時，需要足夠之伸長性以確保手套可拉伸以有助於穿用者之手相當容易地***手套中且不損壞手套。The physical properties of gloves (including synthetic disposable gloves) typically include a suitable snug fit of a thin elastic film to promote wearer sensitivity. At the same time, sufficient extensibility is required to ensure that the glove can be stretched to help the wearer's hand fit into the glove fairly easily without damaging the glove.

組合物combination

用於製造用於製造合成手套之彈性膜之組合物包括合成聚合物、硫及金屬氧化物交聯劑，該組合物中之總固體濃度係介於該組合物之5重量%與20重量%之間。總固體含量之百分比(TSC%)可改變。該等固體較佳以水稀釋至該濃度。The composition for making an elastic film for the manufacture of synthetic gloves comprises a synthetic polymer, sulfur and a metal oxide crosslinker, the total solids concentration in the composition being between 5% and 20% by weight of the composition. between. The percentage of total solids content (TSC%) can vary. These solids are preferably diluted to this concentration with water.

合成聚合物Synthetic polymer

主要合成聚合物可為單一聚合物或2或2種以上聚合物之組合。合適之聚合物之實例係羧酸化聚丙烯腈丁二烯、聚異戊二烯、聚氯丁二烯及/或聚胺基甲酸酯。如早先所述，任何可視作具有用於製造合成手套之合適特性之其他彈性聚合物/共聚物均可用於本發明中。The primary synthetic polymer can be a single polymer or a combination of two or more polymers. Examples of suitable polymers are carboxylated polyacrylonitrile butadiene, polyisoprene, polychloroprene and/or polyurethanes. As noted earlier, any other elastomeric polymer/copolymer that can be considered to have suitable characteristics for making synthetic gloves can be used in the present invention.

合成聚合物較佳係含有自由離子型可交聯基團及共價型可交聯基團之聚合物。離子型可交聯基團之一實例係羧酸鹽，且共價型可交聯基團之一實例係如異戊二烯或丁二烯中之雙鍵。較佳地，合成聚合物係羧酸化聚丙烯腈丁二烯。其通常以羧酸化腈乳膠及丁腈(nitrile butadiene)橡膠之混合物來提供。The synthetic polymer is preferably a polymer containing a free ionic crosslinkable group and a covalent crosslinkable group. An example of one of the ionic crosslinkable groups is a carboxylate, and an example of a covalently crosslinkable group is a double bond such as isoprene or butadiene. Preferably, the synthetic polymer is a carboxylated polyacrylonitrile butadiene. It is usually provided as a mixture of a carboxylated nitrile latex and a nitrile butadiene rubber.

將合成聚合物存在之量計為100 phr。組合物之剩餘組份之量係相對於合成聚合物存在之量來計算。The amount of synthetic polymer present was calculated to be 100 phr. The amount of the remaining components of the composition is calculated relative to the amount of synthetic polymer present.

金屬氧化物交聯劑Metal oxide crosslinker

金屬氧化物交聯劑可為單一化合物或化合物之組合。一種合適之金屬氧化物交聯劑係二價金屬氧化物交聯劑。此種二價金屬氧化物交聯劑之合適實例係氧化鉛、氧化鎂、氧化鋇及/或氧化鋅。The metal oxide crosslinking agent can be a single compound or a combination of compounds. A suitable metal oxide crosslinker is a divalent metal oxide crosslinker. Suitable examples of such divalent metal oxide crosslinkers are lead oxide, magnesium oxide, cerium oxide and/or zinc oxide.

在一較佳實施例中，合成聚合物係羧酸化聚丙烯腈丁二烯，且金屬氧化物交聯劑係氧化鋅。在該實施例中，羧酸基團係藉由氧化鋅交聯劑進行離子型交聯。In a preferred embodiment, the synthetic polymer is a carboxylated polyacrylonitrile butadiene and the metal oxide crosslinker is zinc oxide. In this embodiment, the carboxylic acid groups are ionically crosslinked by a zinc oxide crosslinking agent.

金屬氧化物交聯劑存在之量係較佳在0.2-2.0 phr之範圍內，進一步較佳為0.5-1.5 phr，更進一步較佳為0.8-1.6 phr，更佳為0.8-1.2 phr。若在組合物中不存在其他促進劑，則金屬氧化物之量尤其重要。The metal oxide crosslinking agent is preferably present in an amount of from 0.2 to 2.0 phr, further preferably from 0.5 to 1.5 phr, still more preferably from 0.8 to 1.6 phr, still more preferably from 0.8 to 1.2 phr. The amount of metal oxide is especially important if no other promoter is present in the composition.

硫sulfur

硫作為合成聚合物中任何不飽和基團之共價交聯劑而存在於組合物中。如早先所提及，在合成聚合物為羧酸化丁腈之實例中，硫用於共價型交聯不飽和丁二烯。Sulfur is present in the composition as a covalent crosslinker for any unsaturated groups in the synthetic polymer. As mentioned earlier, in the case where the synthetic polymer is a carboxylated butyronitrile, sulfur is used to covalently crosslink the unsaturated butadiene.

硫可以元素硫之形式存在。硫亦可由有機含硫化合物提供，例如TMTD(二硫化四甲基雙甲硫羰醯胺)。然而，諸如此者之硫供體可能促使化學過敏，且當過敏含量係一問題時，在手套製造中較佳保持其最少之使用。Sulfur can exist in the form of elemental sulfur. Sulfur can also be provided by organic sulfur compounds such as TMTD (tetramethyl bis thiocarbamidine disulfide). However, sulfur donors such as this may contribute to chemical allergy, and when the allergic content is a problem, it is preferred to keep the least use in glove manufacturing.

在組合物中所利用之硫之量係適合介於0.01與0.5 phr之間，較佳介於0.05與0.3 phr之間，進一步較佳為0.1 phr。The amount of sulfur utilized in the composition is suitably between 0.01 and 0.5 phr, preferably between 0.05 and 0.3 phr, further preferably 0.1 phr.

組合物之製備Preparation of composition

可藉由將合成聚合物與金屬氧化物交聯劑、硫及任何其他常用添加劑混合來製備組合物。The composition can be prepared by mixing a synthetic polymer with a metal oxide crosslinker, sulfur, and any other conventional additives.

該常用添加劑可包含穩定劑、抗氧化劑、硫化劑、著色劑等。該組合物之製備包含此項技術中已知之步驟，且該組合物可以習知方式製備。舉例而言，合成聚合物可以諸如氫氧化鉀及/或氫氧化鈉之穩定劑溶液稀釋。所用之穩定劑之量視所用之合成聚合物、組合物之pH值及其他因素而定。穩定劑可在0.5至2 phr範圍內，較佳為1.0至1.5 phr，將其以水稀釋，較佳為濾過水。The usual additives may contain stabilizers, antioxidants, vulcanizing agents, colorants, and the like. The preparation of the composition comprises the steps known in the art and the composition can be prepared in a conventional manner. For example, the synthetic polymer can be diluted with a stabilizer solution such as potassium hydroxide and/or sodium hydroxide. The amount of stabilizer used will depend on the synthetic polymer used, the pH of the composition, and other factors. The stabilizer may be in the range of 0.5 to 2 phr, preferably 1.0 to 1.5 phr, which is diluted with water, preferably filtered water.

將該經稀釋之穩定劑溶液添加至合成聚合物中。將混合物之pH值較佳調節至介於8.5至10.5之間，進一步較佳介於9.0至10.0之間。接著可將金屬氧化物交聯劑添加至混合物中，隨後添加硫。The diluted stabilizer solution is added to the synthetic polymer. The pH of the mixture is preferably adjusted to be between 8.5 and 10.5, further preferably between 9.0 and 10.0. A metal oxide crosslinker can then be added to the mixture followed by the addition of sulfur.

視情況可添加習知促進劑，例如鋅二丁基二硫胺基甲酸鹽、鋅巰苯并噻唑(ZMBT)及/或二硫化四甲胺硫甲醯基(TMTD)。二級促進劑較佳添加量為0.1-1.5phr，較佳為0.2-1.0phr，更佳為0.2-0.6phr。例如Wingstal L(對甲酚與二環戊二烯之產物)之抗氧化劑可以0.2-0.6phr、較佳0.3-0.5phr之範圍之量添加。因著色而選擇用以降低最終彈性膜之透明度之顏料(諸如二氧化鈦)，可以1.0-2.5phr、較佳1.5-2.0phr之範圍之量添加，且著色劑亦可以所需之量添加。接著藉由添加水(較佳為濾過水)將混合物稀釋至總固體濃度介於5-20%之間。Conventional accelerators such as zinc dibutyl dithiocarbamate, zinc benzobenzothiazole (ZMBT) and/or tetramethylammoniothiol disulfide (TMTD) may be added as appropriate. The secondary accelerator is preferably added in an amount of from 0.1 to 1.5 phr, preferably from 0.2 to 1.0 phr, more preferably from 0.2 to 0.6 phr. For example, the antioxidant of Wingstal L (product of p-cresol and dicyclopentadiene) may be added in an amount ranging from 0.2 to 0.6 phr, preferably from 0.3 to 0.5 phr. A pigment (such as titanium dioxide) selected to reduce the transparency of the final elastic film by coloring may be added in an amount of from 1.0 to 2.5 phr, preferably from 1.5 to 2.0 phr, and the colorant may be added in a desired amount. The mixture is then diluted by adding water (preferably filtered water) to a total solids concentration of between 5 and 20%.

彈性膜之製造Elastic film manufacturing

彈性膜之製造使用習知設備。所涉及之步驟通常可描述如下：The elastic film is manufactured using conventional equipment. The steps involved can generally be described as follows:

一合適之鑄模，通常為一手套形狀之模子，可首先浸漬於一含有鈣離子之凝結劑貯槽中。該等鈣離子係以硝酸鈣或氯化鈣之形式提供。亦包含諸如金屬硬脂酸鹽(意即硬脂酸鋅或硬脂酸鈣)之濕潤劑及抗黏著劑，其亦可添加至凝結劑中。鈣離子之濃度較佳在1.0至10.0%之範圍內，較佳為5至10%。濕潤劑及抗黏著劑之量視所需濕潤及黏性降低之量而定，且會改變。A suitable mold, usually a glove-shaped mold, can be first immersed in a coagulant storage tank containing calcium ions. These calcium ions are provided in the form of calcium nitrate or calcium chloride. Wetting agents such as metal stearates (i.e., zinc stearate or calcium stearate) and anti-adhesives are also included, which may also be added to the coagulant. The concentration of calcium ions is preferably in the range of 1.0 to 10.0%, preferably 5 to 10%. The amount of humectant and anti-adhesive agent will vary depending on the amount of wetting and viscosity desired and will vary.

在以凝結劑浸漬並塗覆鑄模後，將其乾燥或部分乾燥，且隨後浸漬於含有本發明之組合物之貯槽中，該組合物含有任何常用添加劑。鑄模在浸漬貯槽中歷時一段時間以確保該鑄模經均勻塗覆，但時間不能過長而促使比所必需更厚之塗層。視所需之塗層厚度而定，鑄模在浸漬貯槽中之停留時間係介於1.0至10.0秒之間，較佳為2.0至5.0秒。After being impregnated with a coagulant and coated with a mold, it is dried or partially dried, and then immersed in a sump containing the composition of the present invention, the composition containing any conventional additives. The mold is allowed to immerse in the sump for a period of time to ensure that the mold is uniformly coated, but not too long to promote a thicker coating than necessary. Depending on the desired coating thickness, the residence time of the mold in the impregnation tank is between 1.0 and 10.0 seconds, preferably between 2.0 and 5.0 seconds.

隨後可乾燥並固化鑄模上之塗層。在最終彈性膜由多層製成之情況下，第一塗層大體上經乾燥，且將鑄模上該大體上經乾燥之組合物浸漬於一含有本發明之組合物之第二貯槽中，該組合物可具有與第一貯槽中之組合物不同之濃度。鑄模在第二貯槽中之停留時間係介於 1至10秒之間，較佳為2至5秒。The coating on the mold can then be dried and cured. Where the final elastic film is formed from multiple layers, the first coating is substantially dried and the substantially dried composition is immersed in a second reservoir containing the composition of the present invention on the mold, the combination The substance may have a different concentration than the composition in the first storage tank. The residence time of the mold in the second storage tank is between Between 1 and 10 seconds, preferably 2 to 5 seconds.

每一層之平均厚度係介於最終彈性膜之6%與90%之間，較佳為30%至70%，更佳為40%至65%。每一層之平均厚度視形成最終彈性膜之組合物層之數目而定。最終彈性膜可由1至15層組成，較佳為1至10層，進一步較佳為2至6層。The average thickness of each layer is between 6% and 90% of the final elastic film, preferably from 30% to 70%, more preferably from 40% to 65%. The average thickness of each layer depends on the number of layers of the composition that form the final elastic film. The final elastic film may be composed of 1 to 15 layers, preferably 1 to 10 layers, further preferably 2 to 6 layers.

若製造一多層膜，則該膜中之層愈多，則形成每一層之組合物之% TSC愈低。此係為保持該多層膜之厚度最小。若製造一單層膜，則通常% TSC會較高。舉例而言，若合成手套中有六個組合物層，則每一層之% TSC係在5%至12% TSC之範圍內。若合成手套中有2-3個組合物層，則每一層之% TSC係在10%至20% TSC之範圍內，較佳為13%至16% TSC。If a multilayer film is produced, the more layers in the film, the lower the % TSC of the composition forming each layer. This is to keep the thickness of the multilayer film to a minimum. If a single layer of film is produced, typically the % TSC will be higher. For example, if there are six composition layers in a synthetic glove, the % TSC of each layer is in the range of 5% to 12% TSC. If there are 2-3 composition layers in the synthetic glove, the % TSC of each layer is in the range of 10% to 20% TSC, preferably 13% to 16% TSC.

可進行其他步驟以調整合成手套之製造。可瀝濾該沈積膜以移除可萃取組份(在40至60℃範圍內之熱水中歷時1至5分鐘)。在此瀝濾過程中，可移除大量界面活性劑、離子及任何其他可溶及可萃取組份。接著使沈積膜通過一圓緣/上袖腔室。Additional steps can be taken to adjust the manufacture of the synthetic gloves. The deposited film can be leached to remove the extractable component (1 to 5 minutes in hot water in the range of 40 to 60 ° C). During this leaching process, a large amount of surfactant, ions, and any other soluble and extractable components can be removed. The deposited film is then passed through a rounded/upper sleeve chamber.

隨後在一具有90℃之最小溫度、在90-150℃範圍內之烘箱中，以15分鐘之最少時間，在15-40分鐘範圍內，乾燥並固化該膜。在實例中描述進一步乾燥及固化條件。接著可氯化該膜，繼而在一介於90-150℃之烘箱中，在15與40分鐘之間，進行中和、洗滌、乾燥、固化及硫化。The film was then dried and cured in an oven having a minimum temperature of 90 ° C in the range of 90-150 ° C for a minimum of 15 minutes in the range of 15-40 minutes. Further drying and curing conditions are described in the examples. The film can then be chlorinated and then neutralized, washed, dried, cured and vulcanized in an oven at 90-150 ° C for between 15 and 40 minutes.

最後，將該膜自鑄模剝離，形成一合成手套。Finally, the film was peeled from the mold to form a synthetic glove.

彈性膜Elastic film

視製造方法而定，最終膜可為一多層膜或一單層膜。最終膜之平均厚度較佳在0.01-0.3 mm範圍內，較佳為0.02-0.2 mm，進一步較佳為0.03-0.1 mm，更進一步較佳為0.05-0.10 mm，進一步較佳為0.03- 0.08 mm，更佳為0.05-0.08 mm。Depending on the method of manufacture, the final film can be a multilayer film or a single layer film. The average thickness of the final film is preferably in the range of 0.01 to 0.3 mm, preferably 0.02 to 0.2 mm, further preferably 0.03 to 0.1 mm, still more preferably 0.05 to 0.10 mm, still more preferably 0.03. 0.08 mm, more preferably 0.05-0.08 mm.

可根據ASTM D-412量測本發明之膜性質。在一較佳實施例中，其中膜之平均厚度經量測為0.03-0.10 mm，膜之較佳物理性質如下：最小拉伸強度為14.0 MPa，相對低之300%之模數小於3.0 MPa，及最小伸長為650%。The film properties of the present invention can be measured in accordance with ASTM D-412. In a preferred embodiment, wherein the average thickness of the film is measured to be 0.03-0.10 mm, the preferred physical properties of the film are as follows: the minimum tensile strength is 14.0 MPa, and the relatively low 300% modulus is less than 3.0 MPa. And the minimum elongation is 650%.

由合成手套之最終用途決定膜之所需耐久性。舉例而言，對於非外科用途而言，穿用時間通常低於3小時，更實際上小於2小時。膜之耐久性可受固化條件控制。通常，固化溫度愈高，彈性膜愈耐久。The desired durability of the film is determined by the end use of the synthetic glove. For example, for non-surgical use, the wear time is typically less than 3 hours, more typically less than 2 hours. The durability of the film can be controlled by curing conditions. Generally, the higher the curing temperature, the more durable the elastic film.

關於手套厚度之術語"平均厚度"係指在沿彈性膜層之點處進行三次厚度量測結果之平均值。在袖口、手掌及指尖處進行量測。量測手套之方法可為多層手套，其中"平均厚度"係對製成手套之多層膜之平均厚度的提及。The term "average thickness" with respect to the thickness of the glove means the average of three thickness measurement results at the point along the elastic film layer. Measure at the cuffs, palms, and fingertips. The method of measuring the glove can be a multi-layer glove wherein "average thickness" is a reference to the average thickness of the multilayer film of the glove.

術語"平均厚度"亦用於多層手套中一層之厚度。其以該多層手套之厚度之百分比表示。舉例而言，本發明之多層合成手套之一層的平均厚度，係在袖口、手掌及指尖處量測之一層之平均厚度量測結果，其以總膜厚度之百分比表示(總厚度亦在袖口、手掌及指尖處量測)。The term "average thickness" is also used for the thickness of one layer in a multi-layer glove. It is expressed as a percentage of the thickness of the multilayer glove. For example, the average thickness of one of the layers of the multi-layer synthetic glove of the present invention is the average thickness measurement of one of the layers measured at the cuff, palm and fingertips, expressed as a percentage of the total film thickness (the total thickness is also in the cuff , measurement at the palm and fingertips).

實例Instance

現將參照下列非限制性實例來描述本發明。The invention will now be described with reference to the following non-limiting examples.

實例1Example 1

下列組份係用於製備根據本發明之組合物。The following components are used to prepare the compositions according to the invention.

1.1將羧酸化聚丙烯腈丁腈乳膠置於一混合容器中。1.1 Place the carboxylated polyacrylonitrile butyronitrile latex in a mixing vessel.

1.2製備包括1.0 phr氫氧化鉀之穩定劑之溶液，且以濾過水稀釋。接著將該穩定劑溶液添加至含有羧酸化聚丙烯腈丁腈乳膠之該混合容器中。1.2 A solution comprising 1.0 phr of potassium hydroxide stabilizer was prepared and diluted with filtered water. The stabilizer solution is then added to the mixing vessel containing the carboxylated polyacrylonitrile butyronitrile latex.

1.3將混合物之pH值調節至8.5-10.5。1.3 Adjust the pH of the mixture to 8.5-10.5.

1.4將諸如硫化劑、著色劑之常用添加劑添加至混合容器中。該等成份之量可顯著改變。1.4 Adding common additives such as vulcanizing agents and colorants to the mixing container. The amount of these ingredients can vary significantly.

2.彈性膜之製備。 2. Preparation of elastic film.

2.1連續攪拌根據表1之組合物，歷時3天時間。該時期可在1-5天之間變化，較佳為2-4天。攪拌速度為15 rpm。攪拌速度可在10-20 rpm之間變化。2.1 The composition according to Table 1 was continuously stirred for 3 days. This period can vary between 1-5 days, preferably 2-4 days. The agitation speed was 15 rpm. The agitation speed can vary between 10-20 rpm.

2.2以濾過水將組合物稀釋至所需濃度，以達到5-20%總固體含量。製備特定固體含量為13% TSC及16% TSC之實例。2.2 Dilute the composition to the desired concentration with filtered water to achieve a total solids content of 5-20%. Examples of specific solids content of 13% TSC and 16% TSC were prepared.

將組合物轉移至一浸漬貯槽中，該組合物已經冷卻或加熱至25-45℃之間之溫度。第一貯槽中之溫度係介於35-45℃之間，較佳介於38-42℃之間。The composition is transferred to a dip tank which has been cooled or heated to a temperature between 25-45 °C. The temperature in the first tank is between 35-45 ° C, preferably between 38-42 ° C.

2.3將一乾淨浸漬鑄模浸漬於一由鈣離子組成之凝結劑貯槽中，該等鈣離子充當凝結劑，諸如(硝酸鈣或氯化鈣用於提供鈣離子)。2.3 A clean impregnation mold is immersed in a coagulant reservoir composed of calcium ions, which act as a coagulant such as (calcium nitrate or calcium chloride for providing calcium ions).

鈣離子之濃度係7-9%。該濃度可在1-10%之範圍內變化，較佳為5-10%。隨後於高於150℃之溫度下乾燥該鑄模。The concentration of calcium ions is 7-9%. The concentration may vary from 1 to 10%, preferably from 5 to 10%. The mold is then dried at a temperature above 150 °C.

2.4接著將以凝結劑塗覆之乾燥鑄模浸漬於一含有根據表1之組合物之貯槽中。此第一次浸漬之停留時間係3秒。2.4 The dry mold coated with a coagulant was then immersed in a tank containing the composition according to Table 1. The residence time of this first impregnation was 3 seconds.

2.5於高於150℃之溫度下，在一乾燥腔室中乾燥該第一沈積膜。該第一層之平均厚度係成品之63%。2.5 The first deposited film is dried in a drying chamber at a temperature above 150 °C. The average thickness of the first layer is 63% of the finished product.

2.6接著將該大體上經乾燥之膜浸漬於一第二乳膠浸漬貯槽中，其具有與第一貯槽中之濃度相同之介於13-16% TSC之間的濃度。停留時間係3秒。該第二層之厚度係37%(袖口-33%，手掌-40%及指尖-27%)。2.6 The substantially dried film is then immersed in a second latex impregnated storage tank having a concentration between 13-16% TSC that is the same as the concentration in the first storage tank. The dwell time is 3 seconds. The thickness of the second layer was 37% (cuffs -33%, palms -40% and fingertips - 27%).

2.7若需要多次浸漬，則隨後可重複步驟2.5及2.6之過程。該等實例中未進行此步驟。2.7 If multiple impregnations are required, the procedures of steps 2.5 and 2.6 may be repeated. This step was not performed in these examples.

2.8該沈積膜由隨後於40-60℃之溫度下，在熱水中瀝濾1.0分鐘之兩層組成。2.8 The deposited film consisted of two layers which were subsequently leached in hot water at a temperature of 40-60 ° C for 1.0 minute.

2.9接著藉由通過一圓緣/上袖腔室對該瀝濾膜上袖。2.9 The sleeve is then lapped through a rim/upper sleeve chamber.

2.10在進入氯化腔室之前，將該經上袖及圓緣之膜在最小溫度為90℃之烘箱中乾燥並固化最少15分鐘，該溫度沿烘箱長度在90-150℃之間變化。2.10 Prior to entering the chlorination chamber, the film of the upper sleeve and the rounded edge was dried and cured in an oven at a minimum temperature of 90 ° C for a minimum of 15 minutes, which temperature varied between 90-150 ° C along the length of the oven.

2.11隨後直接在一氯化腔室中，以800-1000 ppm之游離氯(l )之氯溶液氯化該大體上經乾燥之膜，歷時約25秒。此可在600-1300 ppm之游離氯(l )之間及20-60秒之間變化。氯化過程愈長，氯化過程中所需之氯濃度愈低。2.11 The substantially dried film is then chlorinated directly in a chlorination chamber with a chlorine solution of 800-1000 ppm free chlorine ( 1 ) for about 25 seconds. This can vary between 600-1300 ppm free chlorine ( 1 ) and between 20-60 seconds. The longer the chlorination process, the lower the chlorine concentration required in the chlorination process.

2.12接著中和並洗滌該經氯化及大體上經乾燥之膜，隨後送入另一乾燥腔室中。中和及洗滌之總時間為約35秒。此可在20至60秒之間變化。2.12 The chlorinated and substantially dried film is then neutralized and washed and subsequently sent to another drying chamber. The total time for neutralization and washing is about 35 seconds. This can vary between 20 and 60 seconds.

2.13接著將經氯化、中和及洗滌之膜在烘箱腔室中乾燥、固化及硫化。此實例之固化條件於下表2中提供。該烘箱之溫度係介於90至150℃之間。2.13 The chlorinated, neutralized and washed film is then dried, solidified and sulphur in an oven chamber Chemical. The curing conditions for this example are provided in Table 2 below. The temperature of the oven is between 90 and 150 °C.

2.14乾燥、固化及硫化之總時間係介於15-40分鐘之間。2.14 The total time for drying, curing and vulcanization is between 15-40 minutes.

2.15在藉由一連續輸送器鏈系統完成所有氯化、中和、乾燥及固化之處理後，接著將膜自鑄模剝離。2.15 After all of the chlorination, neutralization, drying and curing treatments have been carried out by a continuous conveyor chain system, the film is then peeled from the mold.

隨後在下列條件下固化表1之組合物。The composition of Table 1 was then cured under the following conditions.

上述膜產生自平滑/無紋理之表面鑄模。當所利用之鑄模係粗糙時，平均厚度量測結果可比以上給出之量測結果大約大10-25%。舉例而言，對於一提供平均厚度為0.07 mm之膜之平滑/無紋理的鑄模而言，一粗糙/有紋理之鑄模將提供平均厚度為0.08 mm之膜。The above film is produced from a smooth/untextured surface mold. When the mold used is rough, the average thickness measurement can be about 10-25% larger than the measurement results given above. For example, for a smooth/untextured mold that provides a film having an average thickness of 0.07 mm, a rough/textured mold will provide a film having an average thickness of 0.08 mm.

以上結果清楚地顯示所有上述膜滿足ASTM D-412之要求。The above results clearly show that all of the above films meet the requirements of ASTM D-412.

如上表中清楚地顯示，即使膜之拉伸強度相對高，為獲得良好之耐久性，仍需要較高之溫度。於較低溫度下固化之膜1-1、1-2及1-5之實例顯示較低之耐久性。As clearly shown in the above table, even if the tensile strength of the film is relatively high, a higher temperature is required in order to obtain good durability. Examples of films 1-1, 1-2, and 1-5 cured at lower temperatures showed lower durability.

實例2Example 2

對於下列調配物，重複實例1之方法，該調配物中包含促進劑ZDBC，二丁基二硫代胺基甲酸鋅。The procedure of Example 1 was repeated for the following formulation, which contained the promoter ZDBC, zinc dibutyldithiocarbamate.

固化條件如下： The curing conditions are as follows:

以下提供顯示彈性膜之物理性質之結果： The results showing the physical properties of the elastic film are provided below:

耐久性試驗結果如下顯示於表9中。該等試驗係於22-37℃之間之溫度及37-99%之濕度下進行。The durability test results are shown in Table 9 below. The tests were carried out at a temperature between 22 and 37 ° C and a humidity of 37-99%.

以上結果表明自穿用手套至缺陷開始出現之時刻之時間。自上表，吾人可斷定於較低溫度下固化之膜之耐久性導致較低之耐久性。於較高溫度下固化之手套較耐久。The above results indicate the time from the wearing of the glove to the moment when the defect begins to appear. From the above table, we can conclude that the durability of the film cured at lower temperatures results in lower durability. Gloves that cure at higher temperatures are more durable.

1.改良崔式(DRAIZE)-95' 試驗。1. Improved Cui type (DRAIZE)-95 ' test. 目的purpose

為評估在成品合成橡膠手套中是否存在一定含量之殘餘化學添加劑，該含量可在未致敏之普通使用者群體中誘發IV型過敏。該試驗中所利用之手套係由實例1之組合物製成。此實例之手套之物理性質如下： To assess whether a residual amount of residual chemical additive is present in the finished synthetic rubber glove, this level can induce Type IV allergy in a population of unsensitized general users. The gloves utilized in this test were made from the composition of Example 1. The physical properties of the gloves of this example are as follows:

研究程序Research procedure

該研究分兩個階段進行。在第一階段中，測試一群50個人類受檢者，以評估產品引起刺激或致敏作用之可能性。在第一階段已顯示試驗產品未表現出誘發皮膚刺激之可能性且未顯示致敏能力後，對另外150個個體開始第二階段。The study was conducted in two phases. In the first phase, a group of 50 human subjects were tested to assess the likelihood of the product causing irritation or sensitization. After the first phase has been shown that the test product does not exhibit the possibility of inducing skin irritation and does not show sensitizing ability, the second phase is initiated for another 150 individuals.

誘發階段- 將一最小尺寸為2 cm×2 cm之試驗物品之樣品以內表面與皮膚接觸而施於研究中之每一試驗受檢者。將試驗貼片貼於上背區域，並以非反應性膠帶連續緊固於邊緣上而確保該貼片之完全閉合。 Induction phase - A sample of a test article having a minimum size of 2 cm x 2 cm was applied to each test subject in the study with the inner surface in contact with the skin. The test patch is applied to the upper back area and continuously secured to the edge with a non-reactive tape to ensure complete closure of the patch.

該試驗之誘發階段包含十片試驗物品在每個星期一、星期三及星期五之施用。每48小時移除試驗物品，並在相同部位換上一新試驗物品，歷時共十次替換。星期五施用之貼片在星期一移除。The induction phase of the trial included the application of ten test articles on each Monday, Wednesday and Friday. The test article was removed every 48 hours and a new test article was replaced at the same location for a total of ten replacements. The patch applied on Friday was removed on Monday.

休息期Rest period

在三週誘發期結束後，移除試驗物品，且在隨後之三週內不再將試驗物品施於試驗受檢者，直至施用激發貼片。After the end of the three-week induction period, the test article was removed and the test article was no longer applied to the test subject for the next three weeks until the challenge patch was applied.

激發階段Excitation phase

將兩個最小尺寸為2 cm×2 cm之相同試驗物品之樣品連續施於空白部位歷時各48小時。評估該試驗部位於每一貼片移除時及第二貼片移除後二至四天之反應。Two samples of the same test article having a minimum size of 2 cm x 2 cm were continuously applied to the blank portion for 48 hours each. The test portion was evaluated for two to four days of reaction upon removal of each patch and removal of the second patch.

試驗受檢者選擇/研究群體Test subject selection/study group

以最少200個未致敏之成人受檢者完成該試驗。此具有所有陰性結果之樣品尺寸提供95%之置信度，在使用者群體中，預期合成橡膠手套(NBR)之化學致敏作用可能性小於1.5%。The trial was completed with a minimum of 200 unsensitized adult subjects. This sample size with all negative results provides 95% confidence that the chemical sensitization potential of synthetic rubber gloves (NBR) is expected to be less than 1.5% in the user population.

結果result

兩百個受檢者完成該研究之兩個階段。161個受檢者係亞洲人(80.5%)、35個受檢者係白種人(17.5%)且四個受檢者係非裔加勒比海人(2%)。研究受檢者之年齡範圍係介於18至52歲之間(平均26.49±7.4歲)。116個受檢者係棕色皮膚，IV型皮膚(58%)，45個受檢者係淺膚色皮膚，III型皮膚(22.5%)，35個受檢者係白皮膚，I型皮膚(17.5%)且4個受檢者係黑皮膚，VI型皮膚(2%)。102個受檢者係女性(51%)且98個受檢者係男性(49%)。Two hundred subjects completed two phases of the study. 161 subjects were Asian (80.5%), 35 subjects were Caucasian (17.5%) and four subjects were African-American (2%). The age range of the study subjects ranged from 18 to 52 years (mean 26.49 ± 7.4 years). 116 subjects were brown skin, type IV skin (58%), 45 subjects were light skin, type III skin (22.5%), 35 subjects were white skin, type I skin (17.5%) And 4 subjects were black skin, type VI skin (2%). 102 subjects were women (51%) and 98 subjects were male (49%).

在誘發階段及激發階段期間，所有該等200個受檢者具有不超過 1.5之最終得分。(參見下表2及3)During the induction phase and the excitation phase, all of the 200 subjects have no more than The final score of 1.5. (See Tables 2 and 3 below)

PP：貼片之前PP: Before the patch 計分標準Scoring standard 貼片試驗診斷標準Patch test diagnostic criteria

結果之解釋Interpretation of the results

此研究以200個未致敏之成人受檢者完成，產生所有陰性結果，因而提供95%之置信度，在使用者群體中，預期合成橡膠手套(NBR)之化學致敏作用可能性小於1.5%。The study was completed in 200 unsensitized adult subjects, yielding all negative results, thus providing 95% confidence that the chemical sensitization potential of synthetic rubber gloves (NBR) is expected to be less than 1.5% in the user population. .

結論in conclusion

無臨床證據表明，在經測試之橡膠手套中存在一定含量之殘餘化學添加劑，該含量可在未致敏之普通使用者群體中誘發IV型過敏症。There is no clinical evidence that a certain amount of residual chemical additive is present in the tested rubber gloves that induces type IV allergy in a population of unsensitized general users.

對200個未致敏之人類受檢者進行測試之此醫學設備，橡膠手套的皮膚致敏作用試驗('改良崔式-95'試驗)係陰性，因此滿足申請專利範圍之要求：如Guidance for Medical Gloves：A Workshop Manual,(FDA 96-4257)中所述，此產品證明降低使用者對化學添加劑致敏之可能性。The medical device for testing 200 unsensitized human subjects, the skin sensitization test of rubber gloves ('modified Cui-95' test) is negative, so it meets the requirements of the patent application scope: eg Guidance for Medical As described in Gloves: A Workshop Manual, (FDA 96-4257), this product demonstrates reduced user susceptibility to chemical additives.

2.對致敏個體之貼片試驗2. Patch test for sensitized individuals 目的purpose

為確定一成品合成橡膠手套是否含有殘餘化學品，該等化學品會在已對下列種類之化學品中的一或多種過敏之個體中引起皮膚反應：噻唑、雙甲硫羰醯胺及胺基甲酸酯。試驗中所利用之手套與改良崔式試驗中所使用之手套相同。To determine if a finished synthetic rubber glove contains residual chemicals, these chemicals can cause skin reactions in individuals who are already allergic to one or more of the following types of chemicals: thiazole, bis-methylthiocarboximine and amine Formate. The gloves used in the test were the same as those used in the modified Cui test.

研究程序：Research procedure:

將一最小為2 cm×2 cm之試驗物品之樣品施用於25個人類受檢者之每一者，該等受檢者先前經診斷對含有醫學設備之NR中之三種已知化學致敏劑中的一或多種過敏：雙甲硫羰醯胺、胺基甲酸酯及噻唑。在人類皮膚上試驗橡膠手套之內部。在此試驗程序中，以所有邊緣連續緊固來施用貼片，且以非反應性膠帶確保完全閉合，歷時48小時。在貼片移除時及隨後之二至四天評估該試驗部位。A sample of a test article of at least 2 cm x 2 cm was applied to each of 25 human subjects who were previously diagnosed with three known chemical sensitizers in NR containing medical equipment. One or more of the allergies: bis-methyl carbonyl carbamide, urethane and thiazole. Test the inside of rubber gloves on human skin. In this test procedure, the patch was applied with continuous fastening of all edges and a complete closure was ensured with a non-reactive tape for 48 hours. The test site was evaluated at the time of patch removal and two to four days thereafter.

試驗受檢者選擇/研究群體Test subject selection/study group

為此研究選擇如下試驗受檢者：根據北美接觸性皮炎研究團體(North American Contact Dermatitis Research Group，NACDRG)之標準計分("Am.J.Contact Dermatitis" 2：122-129,1991)，其患有最小評分為1.5之預診斷過敏症；(對橡膠化學品，雙甲硫羰醯胺、胺基甲酸酯及噻唑)。For this study, the following test subjects were selected: according to the North American Contact Dermatitis Research Group (NACDRG) standard scoring ("Am. J. Contact Dermatitis" 2: 122-129, 1991), Pre-diagnosed allergies with a minimum score of 1.5; (for rubber chemicals, bis-methylthiocarboximine, urethane and thiazole).

結果result

25個患有對雙甲硫羰醯胺、胺基甲酸酯及噻唑有預診斷過敏症之試驗受檢者完成此研究。Twenty-five test subjects with pre-diagnostic allergies to bis-methionine, urethane and thiazole completed the study.

該等受檢者已對以上橡膠化學品之最少一種或所有三種致敏，且該等橡膠化學品之敏感水平得分之範圍係介於1.5至4.0之間。在閉合貼片試驗程序中，每一預診斷對試驗樣品過敏之受檢者之每一次觀察的最終得分為零，因此陰性貼片試驗取得結果。The subjects have sensitized at least one or all three of the above rubber chemicals, and the sensitivity level scores of the rubber chemicals range from 1.5 to 4.0. In the closed patch test procedure, the final score for each observation of each pre-diagnosis tester is all zero, so the negative patch test yields results.

計分標準Scoring standard 貼片試驗診斷標準Patch test diagnostic criteria 計分標準- 根據下列標準對反應強度進行計分：Scoring Criteria - The intensity of the reaction is scored according to the following criteria:

若反應包含所述之皮膚反應，則將補充得分與基本得分相加。最終得分係基本與補充得分之和。If the response contains the skin response, the supplemental score is added to the base score. The final score is the sum of the basic and supplementary scores.

結果之解釋Interpretation of the results

該研究以25個經診斷確定對合成橡膠手套中之下列化學致敏劑中的一或多種過敏之個體完成：雙甲硫羰醯胺、胺基甲酸酯或噻唑。此具有所有陰性結果之樣品尺寸提供95%之置信度，預期經測試之合成橡膠醫藥產品上之化學品，雙甲硫羰醯胺、胺基甲酸酯及/或噻唑在小於11.3%之致敏個體中引起反應。The study identified 25 chemical sensitizers in synthetic rubber gloves with 25 diagnostics One or more of the allergic individuals are completed: bis-methyl carbonyl carbamide, urethane or thiazole. This sample size with all negative results provides 95% confidence that the chemical on the tested synthetic rubber pharmaceutical product, bis-methylthioketamine, urethane and/or thiazole is less than 11.3% A sensitive individual causes a reaction.

結論in conclusion

無臨床證據表明，經測試之合成橡膠手套含有可引起個體之皮膚反應的殘餘化學品，該等個體已對下列橡膠化學品過敏：噻唑、雙甲硫羰醯胺及胺基甲酸酯。此組中所有25個經測試個體均呈現陰性結果(基於所述之計分標準，得分小於1.0)，因此滿足申請專利範圍之降低誘發反應可能性之先決條件。There is no clinical evidence that the tested synthetic rubber gloves contain residual chemicals that can cause skin reactions in individuals who are allergic to the following rubber chemicals: thiazole, bis-methylthiocarboximine and urethane. All 25 tested individuals in this group presented negative results (based on the stated scoring criteria, scores less than 1.0), thus meeting the pre-requisites for reducing the likelihood of evoked response in the scope of the patent application.

應瞭解熟習本發明之此項技術者可在不脫離本發明之範疇的情況下作許多修改。It will be appreciated that those skilled in the art can make many modifications without departing from the scope of the invention.

在隨後之申請專利範圍及本發明之先前描述中，除了因表達語言或必要之含意而上下文另外需要外，詞語"包括"係用於包含之含義，意即在本發明之各種實施例中，用以指定所述特徵之存在，而非排除其他特徵之存在或添加。In the following claims, and in the foregoing description of the present invention, the word "comprising" is used in the meaning of the meaning, Used to specify the existence of the feature, and not to exclude the presence or addition of other features.

Claims

一種用於製造一彈性膜之組合物，其包括：合成聚合物，硫，及金屬氧化物交聯劑，其中該組合物中之總固體濃度係介於該組合物之5-20重量%之間，及其中該金屬化物交聯劑之量係在0.8至2.0phr範圍內。 A composition for making an elastic film comprising: a synthetic polymer, sulfur, and a metal oxide crosslinking agent, wherein the total solid concentration in the composition is between 5 and 20% by weight of the composition The amount of the metallization crosslinker, and the amount thereof, is in the range of 0.8 to 2.0 phr.

如請求項1之組合物，其中該合成聚合物係選自由羧酸化聚丙烯腈丁二烯、聚異戊二烯、聚氯丁二烯及/或聚胺基甲酸酯組成之群之聚合物的一者或混合物。 The composition of claim 1, wherein the synthetic polymer is selected from the group consisting of carboxylated polyacrylonitrile butadiene, polyisoprene, polychloroprene, and/or polyurethane. One or a mixture of things.

如請求項2之組合物，其中該合成聚合物係羧酸化聚丙烯腈丁二烯。 The composition of claim 2, wherein the synthetic polymer is a carboxylated polyacrylonitrile butadiene.

如請求項1之組合物，其中該金屬氧化物交聯劑係二價金屬氧化物。 The composition of claim 1, wherein the metal oxide crosslinking agent is a divalent metal oxide.

如請求項4之組合物，其中該二價金屬氧化物係選自由氧化鉛、氧化鎂、氧化鋇及氧化鋅組成之群之試劑的一者或混合物。 The composition of claim 4, wherein the divalent metal oxide is selected from the group consisting of one or a mixture of agents consisting of lead oxide, magnesium oxide, cerium oxide, and zinc oxide.

如請求項5之組合物，其中該金屬氧化物係氧化鋅。 The composition of claim 5, wherein the metal oxide is zinc oxide.

如請求項8之組合物，其中該金屬氧化物交聯劑之量係0.8-1.2phr。 The composition of claim 8 wherein the amount of the metal oxide crosslinker is from 0.8 to 1.2 phr.

如請求項1之組合物，其中該硫之量係自0.01至0.50phr。 The composition of claim 1 wherein the amount of sulfur is from 0.01 to 0.50 phr.

如請求項1之組合物，其中該組合物不含促進劑。 The composition of claim 1 wherein the composition is free of a promoter.

一種用於製造一彈性膜之組合物，其包括：合成聚合物，硫，及金屬氧化物交聯劑，其中該組合物中之總固體濃度係介於該組合物之5-20重量%之間，及在不含促進劑之該組合物中之交聯劑之量係自0.8至2.0phr範圍內。 A composition for producing an elastic film comprising: a synthetic polymer, sulfur, and a metal oxide crosslinking agent, Wherein the total solids concentration in the composition is between 5 and 20% by weight of the composition, and the amount of crosslinking agent in the composition without the accelerator is in the range of from 0.8 to 2.0 phr.

一種製造一層狀彈性膜之多次塗覆方法，其包括以下步驟：(i)將一鑄模浸漬於根據請求項1之組合物中，以製造一層彈性膜(ii)乾燥該彈性膜組合物；(iii)將該鑄模浸漬於根據請求項1之組合物中；(iv)視需要重複該乾燥步驟(ii)及該額外之浸漬步驟(iii)；及(v)乾燥並固化該層狀彈性膜，其中每一層之平均厚度係自6%至90%且整體層狀彈性膜之平均厚度係自約0.01mm至約0.3mm之間。 A multiple coating method for producing a layered elastic film, comprising the steps of: (i) immersing a mold in the composition according to claim 1 to produce an elastic film (ii) drying the elastic film composition (iii) immersing the mold in the composition according to claim 1; (iv) repeating the drying step (ii) and the additional impregnation step (iii) as needed; and (v) drying and curing the layer The elastic film, wherein each layer has an average thickness of from 6% to 90% and the overall layered elastic film has an average thickness of from about 0.01 mm to about 0.3 mm.

如請求項11之方法，其於步驟(i)前進一步包括(a)將該鑄模浸漬於一含有鈣離子之凝結劑中，其中鈣離子之濃度自1至10重量%之間；接著(b)將該經凝結劑浸漬之鑄模乾燥或部分乾燥。 The method of claim 11, further comprising, before step (i), (a) immersing the mold in a coagulant containing calcium ions, wherein the concentration of calcium ions is between 1 and 10% by weight; and then (b) The coagulant-impregnated mold is dried or partially dried.

如請求項11之方法，其中該組合物包括含有自由離子型可交聯基團及共價型可交聯基團之聚合物。 The method of claim 11, wherein the composition comprises a polymer comprising a free ionic crosslinkable group and a covalent crosslinkable group.

如請求項11之方法，其中該乾燥步驟(ii)及該額外之浸漬步驟(iii)係重複至少一次。 The method of claim 11, wherein the drying step (ii) and the additional impregnation step (iii) are repeated at least once.

如請求項11之方法，其中該膜有2至15層。 The method of claim 11, wherein the film has from 2 to 15 layers.

如請求項15之方法，其中該膜有2至6層。 The method of claim 15, wherein the film has from 2 to 6 layers.

如請求項16之方法，其中該膜有兩或三層。 The method of claim 16, wherein the film has two or three layers.

如請求項17之方法，其中每一層之該平均厚度係整體層狀彈性膜平均厚度之30-70%。 The method of claim 17, wherein the average thickness of each layer is 30-70% of the average thickness of the overall layered elastic film.

如請求項11之方法，其中該鑄模係一手形鑄模，且該彈性膜係一手套之形狀。 The method of claim 11, wherein the mold is a one-hand mold, and the elastic film is The shape of the glove.

一種藉由如請求項11之方法所製造之層狀彈性膜。 A layered elastic film produced by the method of claim 11.

一種製造如請求項1之彈性膜之方法，其包含以下步驟：(i)將一鑄模浸漬於該組合物中，以於該鑄模上製造一層彈性膜；及(ii)乾燥並固化該彈性膜組合物。 A method of producing the elastic film of claim 1, comprising the steps of: (i) immersing a mold in the composition to form an elastic film on the mold; and (ii) drying and curing the elastic film combination.

如請求項21之方法，其於步驟(i)前進一步包括(a)將該鑄模浸漬於一含有鈣離子之凝結劑中，其中鈣離子之濃度係1至10重量%；接著(b)乾燥或部分乾燥該經凝結劑浸漬之鑄模。 The method of claim 21, further comprising, prior to step (i), (a) immersing the mold in a coagulant containing calcium ions, wherein the concentration of calcium ions is from 1 to 10% by weight; and then (b) drying Or partially drying the coagulant-impregnated mold.

一種由層狀彈性膜製成之合成手套，其包括：多層之如請求項1之組合物，其中該組合物經固化及該彈性膜之該平均厚度係約0.01至約0.3mm。 A synthetic glove made of a layered elastic film comprising: a plurality of layers of the composition of claim 1, wherein the composition is cured and the average thickness of the elastic film is from about 0.01 to about 0.3 mm.

如請求項23之合成手套，其中該彈性膜之平均厚度係約0.05至約0.10mm。 The synthetic glove of claim 23, wherein the elastic film has an average thickness of from about 0.05 to about 0.10 mm.

一種如請求項1之組合物用於製造手套的用途。 A use of the composition of claim 1 for the manufacture of a glove.

如請求項25之用途，其中與一習知手套相比，該手套降低皮膚刺激。 The use of claim 25, wherein the glove reduces skin irritation as compared to a conventional glove.

一種藉由如請求項1之組合物所製造之手套，其特徵在於當與一習知手套相比時，其在使用中降低皮膚刺激。A glove made by the composition of claim 1 characterized in that it reduces skin irritation during use when compared to a conventional glove.